Drying oil composition



Patented Nov. 4, 1952 menge; oIYL coMPQsITIvoN: Hermansilochl Chicago,and EdWardM Gleisen Downers l Bred. l

alienware Grove1.1L,Y assignors; 'tolUniretsal 01!4 ,Comnl'liyihicageIll.;A awcorpora nl, l

No Drawing'. Application October 28;,` 1951!, "SverialNm 192,836; Y

13 Clilll (CL 2,59%?? invention relates.; t. A, improyed dry-ing oilfor.. use in synthtiq @dating compositions, inwhichdryingoils;areclistomarlly.employedorref quired said dryingtoilcornrnrisirig-Av a mixture of high molecular. Weight, organic.compounds.` de: riyedlfrcm atleast. two components, one of. which iszaLfatty. acid ester andltheother, a cyclic, nonarornatic hydrocarbonhaving multiple, conjugated olefinicdouble bonds.. Moresneciflcally,theinvention concerns, a drying oil composition hai/.ing superiordryingK `dilalitias in its. capacity to .undergo rapid oxidative,drying, when exposed to.` tmosnheric oxygen to. form a, dried iilrn. oigrea ,..r hardness; and toughnessthan the uri,- saturated fatty ,acidiglyceride or unsatiiraiyed` hyf drocarbon drying oil components arecapable of producing individuallyy the unsatdratedA hydrocarbon dryingoil component bei-ngl selected from theclass characterized as hydroca onconinnct polymersV andthe Yfattyacid; este rying oil being selected fromthe class. cnara ctferizedY as.` styrenated unsaturated, fatty acid;esters, combined in a. specified manner as hereinafter provided- One, orthe principal factors. involved in the oxidatiye .drying oiv a thin lilmof `drying oilupon exposllreof the film. toiatnlospllcrio oxygen and a,factor which. is. belieyed to be,reso.onsilolc for the development ordesirabletollghnees andhardnessi in the ultimate drie nlrn, as.. Well.as being orieof. theprimary contributing factoreA deter-V mining. thedrying. rate for the oil. is: tile nlllnber ofunctionalsubstituentslin,tbemolecillar,strucf tune. the drying. oil molecule Afunctional groupsin a drying oilmolccllleis a ChoinicalY group capableof` ready. conversion to. a radical which benomea the" centerV ofpolymerization and/or oxidationactiyity when the drying oilii4 exposedto atmospheric oxygen. tneradicalgenerally*cornbining. in some'` manner;with a molecule or ariother radical ofthe same, or a, diff-,altem typ@to form a larger aggregate of:V greater molecular weight. Eunotionalityin a. dryingoilJ repre,- sented by such groups.- as.. hydroxyl;radicals, olenic double. bonds, ester linkagesJ carboxyl groups;peroxide groups., etc- Which tend to, actyate the. drying oilv moleculeduring the SQ- calledA dryingprocess;A a. conjugated dienic or trienio.systemvof doublebonde in the hydrocarbon residue of the drying oil19914291416 Consti- Vtuting, one. of the mostl effective poly'fuptgrialVmate. Another factor. of primary, importance in molecular nieightf of`tnedrying. oil molecule sobr jecited. te. oxidativeidryiiie; lecular.Weight, in( gene are the. above. properties the.

tion, formed:by"onfc'oiy thcsoceiflo methodsh inp'rovi'ded,l embodies@applic t'on'qf b t Qf thefaboyefatprs. It isiiofriiH 1 having.. alargenlolecolarwcig'llt and containing multiple. functional ne.berrnoleclllei inclini,- ingnot onlyglyceride.esterilinlraees, but, alsoa relatively" large' number of corlij'ugatqgl olgflrii dubl bondserlmolecllle, One object qf, this,inneritieni.y is toprepare a drying,oil.y composition ,apab oxidative drying Wh oiiyg'entofo'rinfan lti'iilarly.-yalllalolfeif` l 5ati=`rigt l, K I the like. Ahth'r 'objectf vth invention 'is to proydefv@ dylltgaolla @mmm-@i061 9331?@ 1 :ofdry' at i snlieric oisyenltofonn ,vecoating film' which docs kiinderrstrees.. Still t ich. c mloiri ing, prone'ltied of' tY f llljratedA fatty acid .elyoeride drying' oils. withA t e quaiityharaeristics 'l @nu ,curated hydro,- ca'rhpn dry; oil oithilltype,Iesentedby un.- satilratod'hydrooarb c'onl'dnct o mers; the

drying oil compo irable. filing.'` 01m marmi-acidic. Q-lf' d f lcomprises combining an. l1 bp'rrconjulli polymer iliit a, nratetl..fatty acid' r dry sielectedfrom tli'groilp consist cally. admi Lolita tfA more specific embodiment of the invention concerns a process for thepreparation of a drying oil composition which comprises preparing amixture of unsaturated hydrocarbon conjunct polymers having a boilingrange of from about 200 to about 350 C. and a styrenated linseed oilcontaining from about to about 50% of styrene by weight, said mixturecontaining from about 5 to about 25% by weight of said sty-renatedlinseed oil and thermally copolymerizing said mixture at a temperatureof from about 100 to about 350 C. to form said drying oil composition.Another specific embodiment of the invention concerns a drying oilcomposition consisting essentially of at least one component selectedfrom the group consisting of 1) a physical mixture, 2) a thermallycopolymerized mixture, and 3) a catalytically copolymerized mixture offrom about 5 to about 25% of a styrenated unsaturated fatty acid esterdrying oil containing from about 5 to about 50% by weight of styrene,and from about 75 to about 95% by weight of unsaturated conjunct polymerhydrocarbons boiling between about 150 and about 450 C., said polymerscomprising a mixture of polyolenic, cyclic hydrocarbons containingconjugated and non-conjugated unsaturation, having a bromine numberabove about 140 and a maleic anhydride Value of from about 30 to about90 and the individual hydrocarbon components of which have from about2.5 to about 4 double bonds per molecule, from about 40% to about 70% ofwhich are in conjugated relationship to each other.

Other objects and embodiments of this invention relating to specificmethods of preparing said drying oil composition and to particularcomponents thereof will be referred to in greater detail in thefollowing further description of the invention.

The component of the present drying oil composition which lends itsdistinctive properties' carbons containing polyolenic unsaturation inwhich the olenic double bonds are both in conjugated and non-conjugatedrelationship to each other. These hydrocarbons, referred to herein asunsaturated conjunct polymers, when cobodied or copolymerized with astyrenated unsaturated fatty acid ester type of drying oil provide thepresent dryingV oil composition which is particularly desirable in thepreparation of coating compositions, although it is to be emphasizedthat the unsaturated conjunct polymer component need not of necessity becopolymerized or cobodied with the styrenated fatty acid ester componentto obtain the desired advantages herein noted; thus, many of theindicated benefits are obtained by mere physical incorporation of theunsaturated conjunct polymers in the composition as a mixture or insolution with the unsaturated fatty acid ester component. However, thedrying oil compositions prepared by cobodying the unsaturatedhydrocarbon conjunct polymer component and the unsaturated fatty acidester drying oil as well as the corresponding catalytic copolymers ofsaid hydrocarbon and ester drying oils are particularly preferred andconstitute the most effective drying oil compositions provided hereinfrom the standpoint of capacity to undergo oxidative drying to formhard, tough, tack-free, adherent, and rapid-drying films when exposed asa thin liquid film to atmospheric oxygen. Y

Unsaturated conjunct vpolymer hydrocarbons are produced by a processknown to the art as a conjunct polymerization reaction in which anunsaturated non-aromatic hydrocarbon monomer containing at least 3carbon atoms per molecule is contacted with a catalyst generallydescribed as an acid-acting catalyst at reaction conditions suitable toeffect a conjunct polymerization reaction. During the course of thelatter reaction, a sludge-like product forms as one of the principalproducts of the reaction which contains substantially all of thecatalyst initially charged to the reaction combined in the form of aloosely bound addition complex with the desired unsaturated hydrocarbonconjunct polymers. The latter hydrocarbons are recovered from the sludgeby special methods of decomposing the hydrocarbon-catalyst complexescontained in the sludge, as hereinafter described. Suitable unsaturatedhydrocarbon charging stocks to the conjunct polymerization reactioncomprise the monooleiins (for example, propylene and its higherhomologs) the polyolefins (such as butadiene, preferably in admixturewith a suitable monoolen), and/or hydrocarbons containing acetylenicunsaturation, of either straight, branched, or cyclic chain structureand either individually or in admixture with each other. Acid acting orconjunct polymerization catalysts for the production of the desiredunsaturated conjunct polymers are selected from the general class ofsubstances referred to as Friedel-Crafts metal halides and certainmineral acid condensation catalysts. Of these general classes ofcompounds utilizable in the reaction, anhydrous aluminum chloride andaluminum bromide, as well as sulfuric acid and hydrouoric acidcontaining, in each case, less than about 10% by weight of water,preferably the substantially anhydrous acids, effect the conjunctpolymerization reaction most expeditiously. The reaction is carried outby intimately admixing the hydrocarbon charging stock with the catalystat temperatures of from about 30 to about 200 C. preferably at fromabout 0 to about 100 C. and at pressures sucient to maintain thereaction mixture in substantially liquid phase. Optimum production ofthe desired sludge is obtained when the weight proportion of catalyst tohydrocarbon charging stock is from about 0.5 to about 2.5, but thisproportion may be varied over a considerable range of values outside ofthe designated proportions to effect the production of a sludge,although not necessarily with equivalent yields. The products of thereaction are a sludge-phase and an upper layer saturated hydrocarbonphase which separates from the sludge upon standing, the desired sludgephase being recovered therefrom by mere decantation.

Decomposition of the sludge to effect recovery of the unsaturatedhydrocarbon conjunct polymers therefrom may be accomplished by severalalternative procedures, depending upon the catalyst utilized in theconjunct polymerization reaction. One of such methods which may beemployed regardless of the particular conjunct polymerization catalystutilized, consists of hydrolyzing the hydrocarbon-catalyst complexescontained in the sludge by thoroughly admixing the same with water,preferably maintained at a low temperature during the hydrolysis by thepres- @MMS-8.3!

ence-'of` an ice-phaseinr am aqueouehlldrolyzing medium:'Duringitheihydrolysisythe-unsaturated conjunctiihydrocarbon polymers;lassociated4 with -the catalyseinfthesludgeaare released fmmthis.

association and; form :air immiscible upper. layer; Whilethe'Water-solubleA catalyst entersithe` lower aqueous-fphase;`

An alternative `.sludge decomposition. pro cedure, generallyconsideredthe-most economical andithe preferred` method; .utilizablewhen theircataIyst to the-oonjunct .polymerizationireaction isthefvola.-A

` tile' hydrogen.` fluoride catalyst fis byfmeane of thermalidecompositionin'. whichfthegsludgewis heated` untilI the hydrogen:iu'oxide`l is.:` vaporized therefrom. 'A product 1 containing; agreater; de. greeof unsaturationl isobtainediwhenlthersludgeisfthermallyfdecomposediin., the presences oirl a suitablefcatalystwhich= enhances a theV decomposition; such' asfmetallic aparticles.:ofrlead, copper.; cobalt', fand: certainsbrasses. containing copper.;lead i and:v Vtiny particles off graphitic4 carboni` and certainmetallicx fluoridef'and oxyfluoiidesalts,

.The mixture off unsaturated conjunct hydrocarbon-polymers:recoveredgrom::the sludge confsistsfo'ff polyoleniefcyclichydrocarbonsicontaining.y `conjugated and' mon-.conjugated-'unsaturation, of relatively highfmolecularfweig'ht, owide' boiling`rangei but generally. ofhomologousfstructure; the cyclic portion; of theAhydrocarbons-haying-a` cyclopentenyl structure in whichl'the-olenicbondcontained inthe cyclopentene ring is conjugation: 'withl one lormore olenic. lbonds presentin. thel Aalikenyly on alkapolyenyle'sidecha-ins attached. to-the cyclopentene` ring. Theindiividualhydrocarbonsainthemixtureare cyclic;` `alethoughsubstantially; non-aromatic; and contain isolatediunsaturationl in,yaddition-to conjugated unsaturation.. The mixture f off unsaturatedcon.- junct polymer hydrocarbonszboils atia.temperaturefof;from-about'ltto about 450i- C1, has a bromine. numberabove about' 1-40, a maleic anhydride'. value; ofi from aboutl 30` toAabout 90;4 and consists of: hydrocarbons. which. containY lfrom fromabout.;2.5 to abouti 4. double bondsper'mol'ecule, of which;ironia-abouti 401 to` about 70% are in; conjugated relationshipv With,`each other.. Hydrogen tocarbonyatomic.-ratios; of the hydrocarbons.vcontained in the` unsaturated hydrocarbon fractiong vary within;lrelativelyl narrow limits, generally from-about 1.67 =tog aboutA 12,72witnthe actual Weight. percentages of,l h-ydrogenf varying from about12.35 to aboutv 12:6..

The, styuenatedv` unsaturated fatty- 'acidf es llelY drying` oils,utilized in.` the preparationL ofthe present drying oil compositionl,are'y formed a rlprelimi-nary: process by the copolymerizaton of ated toforml one.. for? the primary reactants con template@ in, the `vpresentinvention `include:such semi-dryinef-` iattyr acid. esters as perilla011;. soybean oil; hempseed oil; poppyseedfoil. Ysaillo-wer oil, walnut0.11 ete., `and `particularlythe-olsyse- 6 leeted-VIromrt-hefrapidtdryine: unseturotelilf fatty acid:glyceridesffoonteinine polyenianndlparieu.- Iarlyf coniugatedjpolyepicfunsaturoziion, such; as tung-.f 011;. liriseeld oil; dehydrated;'castors oil. and. oiticlcazoiLL, the preferred membersg ofthe aboveseriesineingf-tupg Qikandzboiled linseedioil- The.stylenatedfunsaturated fatty;l acids themselves derived from; al..naturel;Y elyoerideT and rooovered thereiromzby; hydrolysisafor example;ardoise. utilizable: ini.- tliefpresent. process,- elthooshf. these.arancio., generally preferred; when substantially neutrali.non-.corrosive drying oil.; compositions arpgdesiredionrequired.Copolyrnerizetion of the unsaturated-fattyfacid oresterderivedftherefrom withastyrene tra form@ the. So-called siyrooaied`unsaturatedg-fatty, acids. herein.A utilized es: one of@ theprirneryfne.sortants in,y therpreperation; of thefprnent dryinsroil.composition. may be.; effooted thermally, floyf'l.1.eai'ine; the-styreneand. 1111-. saturated fatty.: acidE ester react'alflslr under;pressure-ii necessary; to maintain substantially liquid phaseeonditionsto a temperature. of from about 50? iofehoutzm CJ: or, .os-.-preferred herein. ootalytioally; by; heating; the;A reactants in thepresenceoir ayoatalyst@ capable of yielding-afree radicallin` tno.1reaction; mixture, Such es eperoxv idi.ofnolymerization,catalyst`Inordentoprepere a dmingg oil: suitable fore theprocess of thapresentinvention by either thermal ort-catalytic copo lyufxierizaton4 ofstyrene., with the; unsaturated fatty acid eisten fromr about 5to`about.50%fby Weight oi-A the `reaction:` mixture -is styrene,resultillggnv theformation oi a-.copolymerA product containing; a.oorrespondingl proportion off styrene;

In this process the` mixture of reactantsisihated .thevvpreferredtmethodoi copolymerization, utilizingarcatalystcapable of yieldinga freeradical inthemixture ot reactants, such. asl a: compound containing. aperoxidioeroup-or aro. linkage, the

formation of. the, styrenated. oil. may be: eiected atrelatively..lovver` reactionJ temperatures and vat a, more rapid..rate,yielding' a product. of more desirable. physipalpropertesl suoli as a.generally lighter color.4 'rhefpreferred catalysts for'V thelpreparation. o f.. thelstyrenated oil as one. of the .primaryfret-optants.l in the. present process are the 'organic peroxides,including suoli oornpormdsA as di-tert-butyl. peroxide bepzoylperoxide.y escoridole. -iortfbntyll perbenzoate tert-bully.hydroperoxide, and.. the various' ozonidesf and. peroxisles:u obtainedVAby-ozionizine` or oxidizingl isoprene,

diisobutylene, cyclohexene. and other hydrocarbons or. hydrocarbonmixtures. The peroxide mary-be: formed in sito. thereaction mixture.'-by aeretipathe.- unsaturoted fatty eodosterrdrying oil dopingi itscopdlymerizaiionwitn the styrene or in afprelirninery siegeoi: theprocess by; passins air-:on eir-ozonernixbures through. the; dryingcil-atmoderateftemperatures, Qfrthe-aboveperdindin types; otr catalyst:lierzizoyl pe. oxidolor a peroxide: deniyaiiye` formed by oridzine the.un

saturated: glyceridedryina oil .in situ is. generally preferred. in; thepreparation of the; styreneted produce, line peroxidie catelysnifutilised; may fbe-addedrd epilyy tothe-mixture of styrenefendnnseturatedhierttm poid; `glyceride :capta-uta eenerally in amountsofmom about @1.01 toabout: 2%

by weight ofth'e.. reactants',` and` following completiorr'orytheyresulting fcopolmnorzation. re-

action, the residual portions of catalyst which have not reacted withthe copolymer may be allowed to remain in the styrenated oil without.markedly affecting the qualities of the product.

The unsaturated hydrocarbon conjunct polymers, containing as they do alarge number of conjugated and nonconjugated olenic double bonds permolecule are capable of being copolymerized with other unsaturatedcompounds, such as the presentv styrenated unsaturated fatty acid estercopolymers to form a product having a greater molecular weight and alarger total number of olenic bonds per molecule than either theconjunct hydrocarbon polymer or fatty acid ester starting material. Thecopolymer thereby obtained has greater molecular weight which accountsfor dried films of tougher and more elastic properties and is alsocapable of drying to a tougher, solid, non-tacky film in shorter dryingperiods by virtue of the greater unsaturation resident in the structureof the copolymer molecules, the increased number of olefin bondsincreasing the functionality present in the structure of the productwhich, in turn, enhances the drying speed of the resulting copolymers.The particular species of the present drying oil compositions consistingof the thermal or vcatalytic copolymers of a styrenated fatty acid esterand a conjugated hydrocarbon conjunct polymer are particularly desirableas drying oil products, since they are generally superior in dryingproperties to otherwise similar coating compositions containing merelyan unsaturated fatty acid glyceride or other drying oil of either thehydrocarbon or ester type.

It has been found in actual drying tests of compositions prepared by theprocess herein provided and containing varying proportions of theindividual drying oil ingredients, in physical mixtures as well ascobodied mixtures, that when the drying oil composition contains lessthan 5% f the styrenated unsaturated fatty acid ester drying oil,including compositions containing 0%, as well as compositions containingmore than 25% by weight of the styrenated fatty acid ester drying oil,the dried films formed upon exposure of the drying oil composition inthin films to atmospheric oxidation are brittle and non-adherent to thesurface to which the liquid composition is applied; the resulting filmchecks and peels upon application of pressure thereon and in otherrespects produces an undesirable dried film. It is therefore signal tothe successful preparation of a desirable drying oil composition thatthe mixture contain not less than but not more than 25% of thestyrenated unsaturated fatty acid ester drying oil. Within these limitson the composition of the present product, the latter, when utilized ina coating composition yields a product of desirable drying properties,since the components are capable of combining in the optimum proportionsrequired for the production of a suitable protective coating film viapolymerization and oxidation; beyond the above limits on thecomposition, however, that is, when the styrenated fatty acid ester ispresent in the composition in quantities less than 5% by weight of theproduct or more than 25% by Weight thereof, the dried films on oxidativedrying tend to possess the undesirable properties hereinabove noted,particularly brittleness and the tendency to be non-adhesive to thesurface to which the drying oil is applied.

In the preparation of one of the alternative species of drying oilcompositions herein provided, comprising a physical mixture ofunsaturated conjunct polymers and the styrenated fatty acid ester dryingoil these ingredients are merely mixed at normal or room temperatures inthe proportion of from 5 to about 25% of the styrenated fatty acid esterdrying oil to from about 75 to about 95% of the unsaturated hydrocarbonconjunct polymer drying oil until a uniform mixture of the two dryingoils is obtained.

The species of drying oil composition herein referred to as thermallycobodied mixtures of the styrenated fatty acid ester and unsaturatedconjunct polymer hydrocarbon ingredients is prepared by heating themixture of drying oils containing not more than 25% and not less than 5%by weight of the styrenated drying oil ingredient to a temperature offrom about to about 350 C. for a cobodying reaction period of from aboutl/2 to about 6 hours, or until the desired viscosity is obtained,preferably a viscosity of from about 10 to about 40 poises. In theproduction of the thermally cobodied species of drying oil compositionprovided herein, the ingredients are desirably stirred as they areheated to reduce the tendency of the product to discolor as a result ofthe development of excessive skin temperatures of the mixture adjacentto the heating surface of the kettle in which the ingredients areheated. The heating is also desirably effected in a closed vesselcontaining an inert atmosphere of carbon dioxide, nitrogen, or othernon-oxidizing vapor over the surface of the oils undergoing the thermalcobodying reaction, thereby preventing oxidative deterioration of theproduct during the heat bodying reaction. The process results in acopolymerization of the unsaturated reactants, the polymerizationoccurring between the unsaturated bonds of the reactant drying oilmolecules.

The species of drying oil composition referred to herein as a catalyticcopolymer of a styrenated fatty acid glyceride and a mixture ofhydrocarbon conjunct polymers is produced by heating the indicateddrying oil reactants in the presence of a suitable polymerizationcatalyst, selected generally from the broad class of catalyticsubstances known in the art as acid-acting inorganic compounds ormolecular addition complexes thereof with certain oxygen-containingorganic compounds. The styrenated glyceride of an unsaturated fatty acidand the unsaturated conjunct polymer hydrocarbon mixture are mixed inthe above-indicated range of proportions (that is, in amounts sufiicientto form mixtures containing not less than 5 per cent and not more thanabout 25 per cent of the styrenated fatty acid glyceride reactant) andheated in an inert atmosphere, accompanied by vigorous stirring, to atemperature of from about 0 to about 250 in the presence of thepolymerization catalyst, added to the reaction mixture in amounts offrom about 0.1 to about 10 per cent by Weight of the reactants.Catalysts suitable for effecting the copolymerization reaction are, ingeneral, the aforementioned acid-acting inorganic compounds or theiraddition complexes, preferably such catalysts as aluminum chloride,aluminum bromide, ferric chloride, magnesium chloride, zinc chloride,bismuth chloride, nickel chloride and bromide, stannous and stannicchlorides, and other halide salts of the Friedel-Crafts' metal halideclass; certain mineral acids, such as sulfuric and hydrochloric orhydrobromic acid, boron trifiuoride and boron trichloride, as well asothers generally known in the art. One of the preferred catalysts forthe reaction are the :molecular Ladditioncomplexes `of the aboveacid-acting catalysts withforganicoxygen-containing 4compounds such fasrthe ethers,

particularly diethylether, which forms the preferredmonoetheratet'ordioxan'; the alcohols, particularly methanol, ethanoland propanol which form the*mono-al'coholates; fthe carboxylic acids,particularly .formic and: aceticwacids which' form thecorresponding-mono Jcarboxylatesfsuch' as aluminum chloridemonoeacetate; :the ketones, particularly :acetone :which Aformsithexmono-acetonates; the nitroesubstituted iallcanes, lpartici larlynitromethane, nitroethane, etc.; and the esters, particularly:ethylacetate.ethylproprionate etc. One `of .thepreferredcatalystsfofthel latter molecular additionfcomplexes.-iseboronftriuoride mono-ethyletherate 'which'zis utilized in the:reaction mixture intheirpre'ferredLratiotofecatalyst to reactants offrom about f1.UvtoFOfperAcentl by Weight of thefcombined @charging`:stocks: .uFo'l-f' lowing completion of the copolymerization reaction,usually after a reaction period of from about 0.5 to about 6 hours atthe aboveiindicatedctem-' peratures, the catalyst may be removed fromthe product by water or mild caustic washing, as with sodiumcarbonateebicarbonate solutions. A'The product formed by the catalyzedcopolymerization reaction is generally of somewhat lightercolor than thethermal copolymer and may .bei-somewhat more viscous-aswell. @Thecopolymerization is preferably continued `-dntil the productshas aviscosity of from aboutf to about 50 poises, and preferably from vabout-10-tof about -20, although the'latter factor may-generally befvariedbya. suitable choice of; reaction'.cOHditioIis'y toform a productparticularly desirable for v a ispecic purpose.

Each species of theproducts of the present 10 Y l I Preparationofunsaturated'hydrocaibon conjnct jpolymers A ymixture ofunsaturatedhydrocarbon conjunct polymers comprising polyoleiiI- iic.`cyclidhydrocarbons in `which the t olenic unsaturation is .bothconjugated andnonfconjugatedwas preparedby hydrolzi-ng a sludge formedbyreactmgamixture of oleniclhydrocarbons. comprising a. fraction of aco-polymergasoline (theproductof the Amixed polymerization of propyleneandgbutylenemonomers) with hydrogenfluoride,separating asludge phaseMand i thereafter A;hydrolyzing the sludge to recover -rthe vunsaturated`hydroc.erben l conjunct polymers. ,InlV the preductionfof thesehydrocarbons, 22 liters v-(15.5 RgJEofLhe-cpQIymer gasoline havingabromine num-bergof 162Lzand containing monofolenic`hydrooarbonssvarying infmolecular Weight from octene to dodegylenearecharged into a pressure autoclave and rapidly stirred as 9.01'kg'. ofliquid anhydrous hydrogen fiuorideare A.introduced --:into..the.reaetor. Ihe pressure is invention, :whetherpthe A:physical :mixtureof:V

styrenated vunsaiju'rjated Afai'lty :acid r:ester and i the mixture ofunsaturated conjunct polymers, the thermal or catalytic copolymer ofsaid ester and hydrocarbon'fdrying'foilsfirr each l"ofwhich from i5 to:about.25.% 4of: the y'composition ithe ystyre'nated fatty -acidesten islutilizable inta Variety -of-- coatingfcompositions, such-Mas paints andvarnishes, as -ther drying `oil component thereon "The present .productsTarei particularly ffsuitable for this purpose llbeoauseio'f1their=re'si`stance '-toaqueous media-,-v including ialli,ellis-,f`arising jbyvirtue* o'fthe large proportion ofi hydrocarbon-*residue Vinthe molecular composition of the drying oil ingredient. The presentproducts are also particularly effective dryingoil.ingredients:pbecausez:ofctheiri` rapid dryingcharacteristics-zdue;:incpartrtothe large number ofVV conjugated .andnon-conjugated double bonds per molecule) and theiphysicaliappearanceand properties fof thefdried'llm result-4 ing upon exposure of thedrying oi1.as a thin film` l 60 y generally broad 1sco-pefof;'ftheginvention Ein .strict accordance therewith i vmaintained at approximately 205 pounds per square inch and thetemperature at 91 C. as stirring isrcontinuedfor ,aV reaction 1period ofapproximately 1 hour. An upper saturated hydrocarbon phase is separatedafter allowing the reaction -mixture to-settle andY is-'deca-ntedfromthe lower acidic :sludge .layer containing substantially all ofthefhfydrogen fluoride originally charged to the reaction.

- 5,0004 grams :of thesludgelayer separated-from the reactionmixture.was .water-hydrolyzed by allowing thel sludgeV to flow into a mixturelof ice and waterfasthe mixture .wasrapidly stirred, additional ice;being added asthe heat Yof Athe resultant hydrolyzing reaction meltedthe ice.

. 2,170 grams of..a. light colored, sweetgsmelling oil which separate@`from; the .aqueous :phase was A facuon'o'f' th'isdry'ingoii onsistirigof the B25-400 C. fraction of the total mixture when spread as a thinfilm on a test panel (tin-plated f-s'heet steel-)sand allowed to dry for3 days (after whiclnno'substantial further change in film propertiesoccurred) produceda-dryfilm, which a1- though dry to touch, that is,non-tacky and fhard, chippedoffo'fromthe..test panel when the latter wasexed; the dried film when exposed Y to weathering conditions in anaccelerated Weathering test (exposure of the panel to ultraviolet flight[carbon arcl"andintermittent sprays of VWater) discolored rapidly(-within 18 hours),

1 weathering.

checked'and peeled WithinlZ'days of accelerated Adryingoilcompositioncomprising a drying oilmixture was: preparedloy1 mixing variousproportions ',f afstyrenatedl lfattyg'acid e'sterwith the. 325 ,to` 400.`;C.V fractionloffjtheunsaturated conjunct polymer`.,hyfdrfo'carloon'sr` prepared as jindicated 'abovfe Thers'tyrenated'iatty,acid v`ester utilizedfin the;preparation consisted ofthe J.copolymerizationpreduct,of"styreneiand `a mixtureQffdinoleiciaeda-liiwleeiceatiq ,'glweidesr The 1'2 having desirablegloss, toughness, hardness aridcolor stability, which on weathering'tests did not check, peel or tend to yellow,

EXAMPLE II A drying oil composition consisting of the thermal copolymerspecies of the present invention may be prepared by heating tocobodying' ing samples of mixtures by plating tin panels withtemperatures a styrenated mixture of linoleic the mixture to a uniformthickness of film and and linolenic fatty acid glycerides and the 325the resulting panels air-dried at constant temto 400 C. fraction of theunsaturated conjunct perature C.) and humidity (relative humidpolymersprepared as in Example I above. ity: 52%) out of contact with dustparticles. A series of samples containing 1, 5, 10, 25 and Samples werealso prepared containing a stand- 15 28 per cent of the styrenatedglyceride esters is ard paint drier (0.023% Co as cobalt naphthenate,prepared and each sample heated to a uniform 0.014% Mn as manganesenaphthenate and cobodying temperature of 220 C. for 3 to l2 0.067% Pb aslead naphthenate). The folloW- hours, until the cobodied mixture has aviscosity ing table presents the results of the drying tests ofapproximately 15 poises. The viscosity of the on the panel samples: zoresultant copolymers is reduced to 11 poises by TABLE I Properties ofdried drying oil films on tin panels Initial Dust Dried Sward s t d 011H d b P 1 B m @Mami fr m it??? sa, tra as' s? tis- None 1 2 32 4Yellow-tacky.

None l 2 32 5 Yellow-slightly tacky.

None. 1 2 32 0 8 Clear-glossy.

Present 1 1 10 0 7 Do.

None l 2 28 0 6 Do.

Present 1 l 2l 0 l0 Yellow-glossy.

None. 1 2 28 0 7 Do.

Presentl 1 l 3 0 16 Do.

None 1 2 18 6 Clear checked.

Present. l 1 7 l2 Do.

None 1 1 9 0 17 Clear-glossy.

Present 1 1 l 0 18 Do.

1 Brittleness-the ease of cracking on exure of the test panel is apleasure of brittlness, indicated by for films which checked readilyupon slight liexure, -i--l--iindicating the greatest degree ofbrittleness on relatively slght flexure, 0 indicating no brittleness andalso no softness or tackiness oi the film, and indicating a Soft film,deslsntmg a relatively soft film drying inwmpletely t0 a tackycondition.

mixing the required quantity of a solvent naphtha (Skellysolve C,consisting primarily of heptanes) with the cobodied product. Theresultant drying oil samples are thereafter spread to a uniformthickness on tin test panels and dried in a constant temperature (30 C.)constant humidity atmosphere. Inspection of the panels before and afteraccelerated weathering tests provide the data in the following Table II.

TABLE 1I Quality characteristics of thermally copolymerized styrenatedoil conitmct polymer drying oils Maxi- Initial Dust Dry mum Sward B .mstyrenated on oonrennrereent ser, Free, Hard, Hard- Harde AppearanceDays Days Days ness, ness ess K Days 1 2 32 36 4 Dark ed- 3g 3g 5 Dg.tacky 8 0 Cleardd' h 1 2 3 s 1s o Date ls glossy' l 2 3 10 21 D0. 1 1 12 18 Do.

noted that compositions containing more than about 25% of the styrenatedglyceride oil compound tend to check on drying and Were unstable lms onthe test panel (i. e. tended to peel and crack). Compositions containingamounts of the styrenated fatty acid glycerides within the range of fromabout 5% to about 25% by Weight of The data indicate that as thepercentage of styrenated fatty acid ester in the composition increases,the drying rate of the thermal copolymer increases, but the brittlenessof the resulting dried lm likewise increases. The compositionscontaining from 5 to about 25 per cent of styrenated oil, however, dryVto hard films which are the composition, however, produce dried films75 relatively more weather resistant than those conbe substaatiallrreduced l?, prizins; agents Such as activated' Qharl" ril i ritea'eta-icfst,saiyniafaydfaaaeaatoning ta colorofthe thermally cobodiedcomposition may i atment withdecolj `d`jin many uses, such as printingink compositions, the color of the drying oil component is an immaterialfactor.

EXAMPLE III A catalytically copolymerized mixture of a styrenatedunsaturated fatty acid ester and uni saturated conjunct polymerhydrocarbon mixture may be prepared by contacting a Wellstirred mixtureof the drying oil ingredients with a boron trifluoride etheratepolymerization catalyst at a temperature of from about '75 to about 100C. In the preparation of the above drying oil product, a series ofsamples consisting of mixtures of styrenated oil and the B25-400 C.fraction of unsaturated conjunct polymers containing 1, 5, 10, 25 and28% of styrenated oil was contacted with the catalyst by adding theetherate dropwise as the mixture of drying oils was rapidly stirred. Thetemperature was maintained at 75 C. for five hours, following which thereaction mixture was washed successively with diluteV aqueous sodiumcarbonate and water and then distilled at 1.0 mm. mercury pressure toremove volatile products. The residue failing to distill over at 300 C.was reserved as product and consisted of a Viscous, dark red materialwhich was reduced in viscosity with Skellysolve C to l1 poises andapplied in lms of uniform thickness to tin panels. The data in thefollowing TableIII indicate the drying properties of the product.

TABLE III tween about 150 "to about45'0` Q., saidpolymers comprising amixture'of *polyoleiinid l cyclic Vfhydrocarbons' containing conjugatedas Well asn'on- Vconjugated unsaturation, hayinga'bromine number Larm/eaboutira and a marea anhydride value ofifrcm'about "3o to) about '90,thegmdividual hydrocarbon components of which have f an average Aof fromabout 2.5 to about 4 doubleA bonds 'per molejcii'le,lfromlabout-@betoiabout'f'lO percent of whit-.harem conjugatedlreiatifonshiptofach other,... V

'2. The-composition of claiin'l'fiirthercliaracterized ingthat Isaid.mixture of unsaturatedconjurifct'lv ,'fpolymer iliydr'ocarbons consistsof the S25-400 `C. "fraction" ffsaid mixture.

3. The composition of claim 1 further characterized in that said fattyacid ester is linseed oil.

4. A process for the manufacture of a drying oil composition whichcomprises copolymerizing from about 5 to about 25 parts by weight of astyrenated unsaturated fatty acid ester containing from about 5 to about50 per cent by Weight of styrene with from about 'l5 to about -95 partsby weight of a mixture of unsaturated conjunct polymer hydrocarbonsboiling between about 150 to about 450 C., said conjunct polymerscomprising a mixture of polyoleiinic, cyclic hydrocarbons containingconjugated as well as nonconjugated unsaturation and having a brominenumber above about 140 and a maleic anhydride value of from about 30 toabout 90, the individual hydrocarbon components of which have an averageof from about 2.5 to about 4 double bonds per molecule, from about 40 toabout 'l0 per cent of which are in conjugated relationship to eachother.

5. The process of claim 4 further characterized in that said styrenatedfatty acid ester is copolymerized with said unsaturated conjunct Dryingqualities of catalyzed copolymer of unsaturated com'unct polymers andstyrenated linseed oil Maxi- Initial Dust Dry mum Sward Brita styrenatedOil Content, Percent Set, Free, Hard, Hard- Hardnes e Appearance DaysDays Days ness, ness s Days 1 2 32 36 4 Dk. Brown-tac i a; 38 5 Dk D0'ky 1 7 0 Redloss 1 1% 4 7 18 0 D0. g y 1 1% 3 8 20 -i- Red-glossy. 1 1 218 18 Red-brittle.

The above tests indicate the general superiority of the dried filmsprepared from styrenated oilunsaturated conjunct polymer compositionscontaining from 5 to about 25% of the former component, as contrastedwith the compositions containing a lower proportion of styrenated oil(which did not completely dry, but remained tacky after 32 days drying)or a higher proportion of styrenated oil (which dried very rapidly to abrittle film and which checked and peeled during the Weatherometertest).

We claim as our invention:

1. A drying oil composition consisting essentially of from about 5 toabout 25 per cent of a styrenated unsaturated fatty acid ester dryingoil -containing from about 5 to about 50 per cent by weight of styrene,and from about 75' to about 95 per cent by Weight of a mixture ofunsatupolymer hydrocarbon mixture at a temperature of from about toabout 350 C.

6. The process of claim 4 further characterized in that said styrenatedfatty acid esterA is copolymerized with said unsaturated conjunctpolymer hydrocarbon in the presence of an acidic polymerizationcatalyst.

7. The process of claim 6 further characterized in that saidpolymerization catalyst is a molecular addition complex of aFriedel-Crafts halide and an oxygen-containing organic compound.

8. The process of claim 7 further characterized in that said catalyst isa boron trifluoride etherate.

9. The process of claim 6 further characterized in that saidpolymerization is effected at a temperature of from about 0 to about 250C.

@meses f15 10. A drying oil composition as dened in claim 1 furthercharacterized in that the composition is a physical mixture of saidfatty acid ester drying oil and said hydrocarbon polymers.

11. A drying oil composition as defined in claim 1 further characterizedin that the composition is a thermally copolymerized mixture of saidfatty acid ester drying oil and said hydrocarbon polymers.

12. A drying oil composition as defined in claim 1 further characterizedin that the composition is a catalytically copolymerized mixture of saidfatty acid ester drying oil and said hydrocanbon polymers.

HERMAN S. BLOCH. EDWARD M. GEISER.

REFERENCES CITED The following references are of record in the iile ofthis patent:

UNITED STATES PATENTS Number

1. A DRYING OIL COMPOSITION CONSISTING ESSENTIALLY OF FROM ABOUT 5 TOABOUT 25 PER CENT OF A STYRENATED UNSATURATED FATTY ACID ESTER DRYINGOIL CONTAINING FROM ABOUT 5 TO ABOUT 50 PER CENT BY WEIGHT OF STYRENE,AND FROM ABOUT 75 TO ABOUT 95 PER CENT BY WEIGHT OF A MIXTURE OFUNSATURATED CONJUNCT POLYMER HYDROCARBONS BOILING BETWEEN ABOUT 150* TOABOUT 450* C., SAID POLYMERS COMPRISING A MIXTURE OF POLYOLEFINIC,CYCLIC HYDROCARBONS CONTAINING CONJUGATED AS WELL AS NONCONJUGATEDUNSATURATION, HAVING A BROMINE NUMBER ABOVE ABOUT 140 AND A MALEICANHYDRIDE VALUE OF FROM ABOUT 30 TO ABOUT 90, THE INDIVIDUAL HYDROCARBONCOMPONENTS OF WHICH HAVE AN AVERAGE OF FROM ABOUT 2.5 TO ABOUT 4 DOUBLEBONDS PER MOLECULE, FROM ABOUT 40 TO ABOUT 70 PER CENT OF WHICH ARE INCONJUGATED RELATIONSHIP TO EACH OTHER.